DE102017217312A1 - Process for the stabilization of halogen-free thermoplastic polymer recyclates and stabilized plastic compositions and molding compositions and moldings produced therefrom - Google Patents

Abstract

The present invention relates to a process for the stabilization of halogen-free thermoplastic synthetic recyclates or previously damaged plastics against oxidative, thermal and / or actinic degradation. In the process according to the invention, at least one primary antioxidant and / or at least one secondary antioxidant and as component (B) at least one alditol are introduced into a halogen-free thermoplastic as component (A). The inventive method plastic recyclates can be stabilized with high efficiency and in a very environmentally friendly and cost-effective manner against oxidative, thermal and / or actinic degradation. In addition, the present invention also relates to corresponding recyclate-based plastic compositions and molding compositions and moldings produced therefrom. Furthermore, the present invention also relates to stabilizer compositions and their use for the stabilization of halogen-free thermoplastic polymer recyclates against oxidative, thermal and / or actinic degradation.

Description

The present invention relates to a process for the stabilization of halogen-free thermoplastic synthetic recyclates or previously damaged plastics against oxidative, thermal and / or actinic degradation. In the process according to the invention, at least one primary antioxidant and / or at least one secondary antioxidant and as component (B) at least one alditol are introduced into a halogen-free thermoplastic as component (A). The inventive method plastic recyclates can be stabilized with high efficiency and in a very environmentally friendly and cost-effective manner against oxidative, thermal and / or actinic degradation. In addition, the present invention also relates to corresponding recyclate-based plastic compositions and molding compositions and moldings produced therefrom. Furthermore, the present invention also relates to stabilizer compositions and their use for the stabilization of halogen-free thermoplastic polymer recyclates against oxidative, thermal and / or actinic degradation.

Plastic recyclates are a growing market and an important element in the circular economy of raw materials, whereby ideally recyclates should then replace new plastics with an identical or at least comparable property profile. However, in the case of recyclates from the production or of old plastics during the first processing steps (eg compounding, injection molding) and the application to irreversible changes in the polymer chain by mechano-chemical, chemical or light-induced processes (see, eg R. Pfaendner et al., Angew. Makromol. Chemistry 1995, 232, 193-227; J. Pospisil et al., Pol. Degr. Rod. 1995 ). Radical reactions in the presence of oxygen generate new chemical groups in the polymer chain and / or change the composition of the polymer. The concentration of these newly formed groups increases with the time of use and the field of application (UV light, high temperatures, contact media). The structural inhomogeneities of a recycled material influence the plastic properties, such as the mechanical properties.

Furthermore, recyclates or previously damaged plastics are more sensitive to oxidation than virgin material, since decomposition products act as initiator sites for further oxidation or as prodegradants ( AS Maxwell, Pol. Closely. Sci. 2008, 381-385 ; IH Craig, JR White, J. Mater. Sci. 2006, 41, 993-1006 ). In order to achieve a quality improvement of plastic recyclates, the re-stabilization with selected stabilizers is an essential method. The stabilizers used protect the recyclate from further oxidative (or photooxidative) damage. However, the optimized stabilizer composition for a recyclate differs from the stabilizer composition of the virgin product due to the described structural deviations (see eg R. Pfaendner, Kunststoffe international 12/2015, 41-44 ).

• - Stabilisierungs-Zusammensetzung bestehend aus einem phenolischen Antioxidans, einem Phosphit und einem Fettsäuresalz ( EP 0662101 ).
• - Stabilisierungs-Zusammensetzung bestehend aus einem phenolischen Antioxidans, einem Phosphit und einem Metalloxid wie Calciumoxid ( US 6525158 , US 6251972 ).
• - Stabilisierungs-Zusammensetzung bestehend aus einem phenolischen Antioxidans und einem polyfunktionellen Epoxid ( EP 0702704 ).
• - Stabilisierung durch ein makrozyklisches Piperidin ( US 5789470 ).
• - Stabilisierungs-Zusammensetzung bestehend aus einem sekundären aromatischen Amin und einem polyfunktionellen Epoxid ( WO 97/30112 ).
• - Entfärbung von geschädigten Pololefinen durch ein Hydroxylamin ( EP 470048 )
• - Mischung aus Antioxidantien, Gleitmittel, Antiblockmittel, UV-Stabilisatoren und Antistatika für Rezyklatfolien ( DD 288161 )
• - Stabilisierungs-Zusammensetzung für gemischte Kunststoffe bestehend aus einem phenolischen Antioxidans und einem Phosphit/Phosphonit ( EP 0506614 )

Due to the today recognized differences between plastic virgin material and plastic recyclates, special recyclate stabilizer compositions are known and also available as commercial products (eg Recyclostab series from PolyAd Services GmbH, Bensheim). Known technical stabilization solutions that meet the requirements of recyclates are, for example:

• Stabilizing composition consisting of a phenolic antioxidant, a phosphite and a fatty acid salt ( EP 0662101 ).
• Stabilizing composition consisting of a phenolic antioxidant, a phosphite and a metal oxide such as calcium oxide ( US 6525158 . US 6251972 ).
• Stabilizing composition consisting of a phenolic antioxidant and a polyfunctional epoxide ( EP 0702704 ).
• Stabilization by a macrocyclic piperidine ( US 5789470 ).
• Stabilizing composition consisting of a secondary aromatic amine and a polyfunctional epoxide ( WO 97/30112 ).
• Discoloration of damaged pololefins by a hydroxylamine ( EP 470048 )
• - Mixture of antioxidants, lubricants, antiblocking agents, UV stabilizers and antistatics for recycled sheets ( DD 288161 )
• Stabilizer composition for mixed plastics consisting of a phenolic antioxidant and a phosphite / phosphonite ( EP 0506614 )

Despite the known solutions, there is still the need for particularly efficient or effective, environmentally friendly and cost-effective ways of stabilizing plastic recyclates or stabilizer compositions usable therefor.

Recyclates have already gone through a life cycle and were already compounded into plastic moldings and exposed as such, for example, mechanical, chemical, actinic and / or oxidative stress. This results in certain defects in the polymer chain, which cause a further disproportionate damage to the underlying plastic material in a re-processing of the recyclates. The existing damage sites in the polymer serve as initiator sites for accelerated and extended degradation of the polymer. In particular, lowering the molecular weight, broadening the molecular weight distribution, lowering the mechanical properties and increasing the photosensitivity are typical appearances of recycled plastics, especially their re-processing. The overall deteriorated property profile is therefore rather detrimental to reprocessing.

On this basis, it was the object of the present invention to provide a method for stabilizing halogen-free thermoplastic polymer recyclates, with which the plastic recyclates can be stabilized in a very effective, environmentally friendly and cost-effective manner against oxidative, thermal and / or actinic degradation.

This object is achieved in terms of a method for stabilizing halogen-free thermoplastic plastic recyclates with the features of claim 1, in terms of a plastic composition having the features of claim 11, with respect to a molding compound or a molding, which can be produced from the plastic composition having the features of the claim 18, with respect to a stabilizer composition having the features of claim 19 and with regard to the use of the stabilizer compositions having the features of claim 20. The respective dependent claims represent advantageous developments.

1. (A) mindestens ein primäres Antioxidans und/oder mindestens ein sekundäres Antioxidans, und
2. (B) mindestens ein Alditol (Zuckeralkohol) und/oder Cyclitol

in ein halogenfreies thermoplastisches Kunststoff-Rezyklat eingebracht werden. The invention thus provides a process for stabilizing halogen-free thermoplastic synthetic recyclates against oxidative, thermal and / or actinic degradation, in which

1. (A) at least one primary antioxidant and / or at least one secondary antioxidant, and
2. (B) at least one alditol (sugar alcohol) and / or cyclitol

be introduced into a halogen-free thermoplastic plastic recyclate.

According to the present invention, a plastic recyclate is understood to mean a plastic recyclate according to the conceptual definition according to standard DIN EN 15347: 2007. Furthermore, there are relevant international standards for many types of plastic recyclates. For PET plastic recyclates, for example, DIN EN 15353: 2007 is relevant. PS recyclates are in DIN EN 15342: 2008 described in more detail. PE recyclates are in DIN EN 15344: 2008 treated. PP recyclates are characterized in DIN EN 15345: 2008. For the purpose of the corresponding special plastic recyclates, the present patent application makes the definitions of these international standards own.

Plastic recyclates, in contrast to new plastics, usually have a pre-existing damage, ie oxidative or (photo) oxidative processes generate new chemical groups on the polymer chain. In the case of polyolefins, for example, these are predominantly carbonyl groups which are not or only to a very minor extent present in virgin material. The concentration of the carbonyl groups is therefore at the same time a measure of the pre-damage of the polymer. The concentration of carbonyl groups can be determined by known analytical methods such as, for example, infrared spectroscopy, as described, for example, in US Pat E. Richaud et al. Pole. Degr. Rod. 2009, 94, 410-420 is described. Here, a measurement of the absorption of the carbonyl vibration in the range of 1720 cm ^-1 .

By "halogen-free" is meant, according to the invention, that the thermoplastic contains less than 1% of halogen-containing polymers, e.g. PVC or PVDC. Preferably, the halogen-free thermoplastic contains less than 0.5%, more preferably less than 0.1%, of halogen-containing polymers. Most preferably, the halogen-free thermoplastic contains no halogen-containing polymers at all.

In the process according to the invention, component (A), ie the at least one primary antioxidant and / or the at least one secondary antioxidant, and component (B), ie the at least one alditol or cyclitol, are introduced into a halogen-free thermoplastic synthetic material. The components (A) and (B) can be introduced individually or separately from one another into the plastic recyclate or the components (A) and (B) can be used together in the form of a composition containing the components (A) and (B) In the form of a composition consisting of components (A) and (B) are introduced into the plastic recyclate.

• - mindestens ein primäres Antioxidans, oder
• - mindestens ein sekundäres Antioxidans, oder
• - mindestens eine primäres Antioxidans und mindestens ein sekundäres Antioxidans verwendet.

As component (A) becomes

• at least one primary antioxidant, or
• at least one secondary antioxidant, or
• at least one primary antioxidant and at least one secondary antioxidant used.

In the event that at least one primary antioxidant and at least one secondary antioxidant are used, these can also be introduced individually or separately from one another or together in the form of a mixture into the plastic recyclate.

The components (A) and (B) used according to the invention together act as a stabilizer for the halogen-free thermoplastic synthetic material, wherein the presence of both components (A) and (B) leads to oxidative, thermal and / or actinic degradation of the halogen-free thermoplastic polymer. Recycled is inhibited or prevented. In other words, by introducing the components (A) and (B) into the halogen-free thermoplastic polymer recyclate, the plastic is stabilized against oxidative, thermal and / or actinic degradation.

The present invention is characterized in particular by the fact that alditols (sugar alcohols) and / or cyclitols are used together with primary and / or secondary antioxidants for the stabilization of halogen-free thermoplastic polymer recyclates.

Sugar alcohols or polyols have not hitherto been used to stabilize halogen-free thermoplastics or recyclates. Sugar alcohols and polyols are, according to the prior art, only components in formulations for the heat stabilization of polyvinyl chloride (PVC) and other halogen-containing polymers such as polyvinylidene chloride (PVDC) in compositions containing metal soaps as heat stabilizers. This stabilizing effect of polyols in halogen-containing polymers is explained by the fact that chelation and deactivation of the PVC degradation-promoting zinc compounds takes place (see HO Wirth, H. Andreas, Pure Appl. Chem. 1977, 49, 627-648 ; T. lida, K. Goto, J. Appl. Pole. Sci. 1980, 25, 887-900 ) or to achieve a reaction as HCI scavenger in Zn-free PVC (see J. Steenwijk et al. Pole. Degr. Rod. 2006, 2233-2240 ).

From the known mechanisms of the action of polyols in the heat stabilization of halogen-containing polymers such as PVC, however, no conclusion can be made for the effect of a stabilizer in non-halogenated plastics or even recyclates. Rather, these known mechanisms are applicable only to halogen-containing polymers and can not be transferred to halogen-free polymers. Thus, it has not been foreseen but rather surprising that with the present invention it has been found that alditols (sugar alcohols) and / or cyclitols can also stabilize halogen-free polymer recyclates when used together with primary and / or secondary antioxidants become.

According to the invention it has surprisingly been found that by introducing at least one alditol and / or at least one cyclitol and at least one primary and / or at least one secondary antioxidant, a very effective stabilization of halogen-free thermoplastic plastic recyclates against oxidative, thermal and / or actinic degradation can be achieved. In addition, alditols or cyclitols are very environmentally friendly and cost-effective compounds. Thus, the process of the invention halogen-free thermoplastic polymer recyclates can be stabilized in a very effective, environmentally friendly and cost-effective manner against oxidative, thermal and / or actinic degradation.

The inventors suspect that the alditols and / or cyclitols incorporated into the plastic recyclate can react here with the damage sites already present (usually carbonyl groups) to form half or full acetals when the recompounding is carried out. Thus, the Damage sites in the plastic are effectively masked and are no longer available as initiator sites for further degradation. With the method according to the invention or with the additive compositions according to the invention, it is thus possible to eliminate damage sites in recycled plastic recyclates.

The halogen-free thermoplastic recycled material used in the process of the invention is preferably a polyolefin recyclate, e.g. a polypropylene recyclate or a polyethylene recyclate.

Polylefin recyclates whose carbonyl group content, determined by absorption in the infrared spectrum, is at least 0.01 mol / kg, preferably greater than 0.02 mol / kg and particularly preferably greater than 0.05 mol / kg, are particularly suitable for stabilizing pre-damaged recyclates ,

In a preferred variant of the method according to the invention, the at least one primary antioxidant is selected from the group consisting of phenolic antioxidants, amines, lactones and mixtures thereof.

• Alkylierte Monophenole, wie z.B. 2,6-Di-tert-butyl-4-methylphenol, 2-tert-Butyl-4,6-dimethylphenol, 2,6-Di-tert-butyl-4-ethylphenol, 2,6-Di-tert-butyl-4-n-butylphenol, 2,6-Di-tert-butyl-4-isobutylphenol, 2,6-Dicyclopentyl-4-methylphenol, 2-(α-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Dioctadecyl-4-methylphenol, 2,4,6-Tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethyl-phenol, lineare oder verzweigte Nonylphenole, wie z.B. 2,6-Dinonyl-4-methylphenol, 2,4-Dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-Dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-Dimethyl-6-(1'-methyltridec-1'-yl)phenol und Mischungen hiervon;
• Alkylthiomethylphenole, wie z.B. 2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-Dioctylthiomethyl-6-methylphenol, 2,4-Dioctylthiomethyl-6-ethylphenol, 2,6-Didodecylthiomethyl-4-nonylphenol;
• Hydrochinone und alkylierte Hydrochinone, wie z.B. 2,6-Di-tert-butyl-4-methyoxyphenol, 2,5-Di-tert-butylhydrochinon, 2,5-Di-tert-amylhydrochinon, 2,6-Diphenyl-4-octadecyloxyphenol, 2,6-Di-tert-butylhydrochinon, 2,5-Di-tert-butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4-hydroxyphenylstearat, Bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipat;
• Tocopherole, wie z.B. α-, β-, γ-, δ-Tocopherol und Mischungen aus diesen (Vitamin E);
• Hydroxylierte Thiodiphenylether, wie z.B. 2,2'-Thiobis(6-tert-butyl-4-methylphenol), 2,2'-Thiobis(4-octylphenol), 4,4'-Thiobis(6-tert-butyl-3-methylphenol), 4,4'-Thiobis(6-tert-butyl-2-methylphenol), 4,4'-Thiobis(3,6-di-sec-amylphenol), 4,4'-Bis(2,6-dimethyl-4-hydroxyphenyl)disulfid;
• Alkylidenbisphenole, wie z.B. 2,2'Methylenbis(6-tert-butyl-4-methylphenol), 2,2'-Methylenbis(6-tert-butyl-4-ethylphenol), 2,2'-Methylenbis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-Methylenbis(4-methyl-6-cyclhexylphenol), 2,2'-Methylenbis(6-nonyl-4-methylphenol), 2,2'-Methylenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(6-tert-butyl-4-isobutylphenol), 2,2'-Methylenbis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-Methylenbis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylenbis(2,6-di-tert-butylphenol, 4,4'-Methylenbis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 2,6-Bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrat], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadien, Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalat, 1,1-Bis-(3,5-dimethyl-2-hydroxyphenyl)butan, 2,2-Bis(3,5-di-tert-butyl-4-hydroxyphenyl)propan, 2,2-Bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutan, 1,1,5,5-Tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentan;
• O-, N- und S-Benzyl-Verbindungen, wie z.B. 3,5,3',5'-Tetra-tert-butyl-4,4'-dihydroxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercapto-acetat, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetat, Tris(3,5-di-tert-butyl-4-hydroxybenzyl)amin, , Bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalat, Bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfid, Isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetat;
• Hydroxybenzylierte Malonate, wie z.B. Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonat, Dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonat, Didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonat, Bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonat;
• Aromatische Hydroxybenzylverbindungen, wie z.B. 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol, 1,4-Bis(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,3,5,6-tetramethylbenzol, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol;
• Triazinverbindungen, wie z.B. 2,4-Bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxphenylethyl)-1,3,5-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroyphenylpropionyl)hexahydro-1,3,5-triazin, 1,3,5-Tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurat;
• Benzylphosphonate, wie z.B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonat, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Di-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonat, das Calciumsalz des Monoethylesters der 3,5-Di-tert-butyl-4-hydroxybenzylphosphonsäure;
• Acylaminophenole, wie z.B. 4-Hydroxylauranilid, 4-Hydroxystearanilid, Octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamat;
• Ester der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan;
• Ester der β-(5-tert-Butyl-4-hydroxy-3-methylphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan, 3,9-Bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxyl}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro [5.5]undecan;
• Ester der β-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris-(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan;
• Ester der (3,5-Di-tert-butyl-4-hydroxyphenyl)essigsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan;
• Amide der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäure, wie z.B. N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazid, N,N'-Bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamid (Naugard^®XL-1, vertrieben durch Addivant);

As phenolic antioxidants can be used, for example:

• Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2 , 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethyl-phenol, linear or branched nonylphenols, such as, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof;
• Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
• Hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol , 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 -hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxylphenyl) adipate;
• Tocopherols, such as α-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E);
• Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-ol) methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis (2,6- dimethyl-4-hydroxyphenyl) disulfide;
• Alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methylphenol) 6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclhexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4 , 6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2 ' -Methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di tert-butylphenol, 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis ( 5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3) tert -butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-h ydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di tert -butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5 pentan-tert-butyl-4-hydroxy-2-methylphenyl);
• O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate , Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate;
• Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, Didodecylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3, 5 di-tert-butyl-4-hydroxybenzyl) malonate;
• Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl) butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol;
• Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3 , 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl) tert -butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-diisobutyl) tert -butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1 , 3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate;
• Benzyl phosphonates, such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, di-octadecyl-3,5-di-tert-butyl butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
• Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate;
• Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane , 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;
• Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, for example methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane , 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxyl } -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane;
• Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phosphono 2,6,7-trioxabicyclo [2.2.2] octane;
• Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid with mono- or polyhydric alcohols, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha -2,6,7-trioxabicyclo [2.2.2] octane;
• Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N ' Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3 , 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard ^® XL-1, sold by Addivant);

Ascorbic acid (vitamin C).

• Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionat, Pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionat, Tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurat, 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurat, 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzol, Triethylenglycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionat, N,N'-Hexan-1,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionsäureamid.

Preferred phenolic antioxidants are:

• Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. di-tert-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, N propionamide, N'-hexane-1,6-diyl-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl).

Further preferred phenolic antioxidants are phenolic antioxidants based on renewable raw materials such as. As tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, Fisetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid and resveratrol.

More preferably, the phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is used as the primary antioxidant.

• N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylendiamin, N,N'-Bis(1-methylheptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'-Bis(2-naphthyl)-p-phenylendiamin, N-Isopropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'-phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p-Toluolsulfamoyl)diphenylamin, N,N'-Dimethyl-N,N'-di-sec-butyl-p-phenylendiamin, Diphenylamin, N-Allyldiphenylamin, 4-Isopropoxydiphenylamin, N-Phenyl-1-naphthylamin, N-(4-tert-Octylphenyl)-1-naphthylamin, N-Phenyl-2-naphthylamin, octyliertes Diphenylamin, z.B. p,p'-Di-tert-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylaminophenol, 4-Nonanoylaminophenol, 4-Dodecanoylaminophenol, 4-Octadecanoylamino-phenol, Bis(4-methoxyphenyl)amin, 2,6-Di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-Diaminodiphenylmethan, 4,4'-Diaminodiphenylmethan, N,N,N',N'-Tetramethyl-4,4'-diaminodiphenylmethan, 1,2-Bis[(2-methyl-phenyl)amino]ethan, 1,2-Bis(phenylamino)propan, (o-Tolyl)biguanid, Bis[4-(1',3'-dimethylbutyl)-phenyl]amin, tert-octyliertes N-Phenyl-1-naphthylamin, ein Gemisch aus mono- und dialkylierten tert-Butyl/tert-Octyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Nonyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Dodecyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Isopropyl/Isohexyl-diphenylaminen, ein Gemisch aus mono- und dialkylierten tert-Butyldiphenylaminen, 2,3-Dihydro-3,3-dimethyl-4H-1,4-benzothiazin, Phenothiazin, ein Gemisch aus mono- und dialkylierten tert-Butyl/tert-Octylphenothiazinen, ein Gemisch aus mono- und dialkylierten tert-Octylphenothiazinen, N-Allylphenothiazin, N,N,N',N'-Tetraphenyl-1,4-diaminobut-2-en sowie Mischungen oder Kombinationen hiervon.

As aminic antioxidants, for example, can be used:

• N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl- p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p- phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl- N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl -2-naphthylamine, octylated diphenylamine, eg, p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diamine diphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl Butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2, 3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, as well as mixtures or combinations thereof.

• N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylendiamin, N,N'-Bis(1-methylheptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'-Bis(2-naphthyl)-p-phenylendiamin, N-Isopropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'-phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin.

Preferred aminic antioxidants are:

• N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl- p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p- phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.

• Hydroxylamine bzw. N-oxide (Nitrone), wie z.B. N,N-Dialkylhydroxylamine, N,N-Dibenzylhydroxylamin, N,N-Dilaurylhydroxylamin, N,N-Distearyl-hydroxylamin, N-Benzyl-α-phenylnitron, N-Octadecyl-α-hexadecylnitron, sowie Genox EP (vertrieben durch Addivant) gemäß der Formel:
  

Further preferred aminic antioxidants are:

• Hydroxylamines or N-oxides (nitrones), such as N, N-dialkylhydroxylamine, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearyl-hydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl α-hexadecyl nitrone, and Genox EP (sold by Addivant) according to the formula:
  

• Benzofuranone und Indolinone wie z.B. 3-(4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-on, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)-phenyl]benzofuran-2-on, 3,3'-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy]-phenyl)benzofuran-2-on), 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-on, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-on, 3-(3,5-dimethyl-4-pivaloyloxyphenyl )-5,7-di-tert-butyl-benzofuran-2-on, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-on, 3-(2,3-di methylphenyl)-5,7-di-tert-butyl-benzofuran-2-on.

Preferred lactones are:

• Benzofuranones and indolinones such as, for example, 3- (4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4 ( 2-stearoyloxyethoxy) -phenyl] -benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- (2-hydroxyethoxy) -phenyl) -benzofuran-2-one), 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2 -on, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert -butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

A further preferred variant of the method according to the invention is characterized in that the at least one secondary antioxidant is selected from the group consisting of Phosphorus compounds, in particular phosphites and phosphonites, organo-sulfur compounds, in particular sulfides and disulfides, and mixtures thereof.

• Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphosphite, Tri(nonylphenyl)phosphit, Trilaurylphosphite, Trioctadecylphosphit, Distearylpentaerythritoldiphosphit, Tris-(2,4-di-tert-butylphenyl)phosphit, Diisodecylpentaerythritoldiphosphit, Bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphit, Bis(2,4-di-cumylphenyl)pentaerythritoldiphosphit, Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphit, Diisodecyloxypentaerythritoldiphosphit, Bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphit, Bis(2,4,6-tris(tert-butylphenyl)pentaerythritoldiphosphit, Tristearylsorbitoltriphosphit, Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylendiphosphonit, 6-Isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, Bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphit, Bis(2,4-di-tert-butyl-6-methyl-phenyl)ethylphosphit, 6-Fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz-[d,g]-1,3,2-dioxaphosphocin, 2,2'2"-Nitrilo[triethyltris(3,3",5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphit], 2-Ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl))phosphit, 5-Butyl-5-ethyl-2-(2,4,6-tri-tert-butyl-phenoxy)-1,3,2-dioxaphosphiran.

As phosphites or phosphonites, for example, it is possible to use:

• Triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tri (nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, Bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra tert -butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl) butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenz [d, g] -1,3,2-dioxaphosphocine, 2, 2'2 "-nitrilo [triethyltris (3,3 ', 5,5'-tetra-tert-butyl-1,1'- biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5 -butyl-5-ethyl-2- (2,4,6-tri-tert-butyl-phenoxy) -1,3,2-dioxaphosphiran.

• Tris-(2,4-di-tert-butylphenyl)phosphit, Bis(2,4-di-tert-butylphenyl)penta-erythritoldiphosphit, Bis(2,4-di-cumylphenyl)pentaerythritoldiphosphit, Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylendiphosphonit, Bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphit.

Preferred phosphites or phosphonites are:

• Tris- (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di tert-butylphenyl) -4,4'-biphenylene diphosphonite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

Most preferably, the phosphite tris- (2,4-di-tert-butylphenyl) phosphite is used as the secondary antioxidant.

• Distearylthiodipropionat, Dilaurylthiodipropionat; Ditridecyldithiopropionat, Ditetradecylthiodipropionat, 3-(dodecylthio)-1,1'-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propandiyl]propansäureester.

Preferred sulfur compounds are:

• Distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyl dithiopropionate, ditetradecyl thiodipropionate, 3- (dodecylthio) -1,1 '- [2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3-propanediyl] propanoic acid ester.

In a further preferred embodiment, component (A) consists of both a primary antioxidant and a secondary antioxidant. In this case, it is particularly preferable that the component (A) consists of a phenolic antioxidant and a phosphite or phosphonite.

In a further preferred embodiment, the components (A) and (B) consist of a renewable raw material.

According to another preferred variant of the process according to the invention, the at least one alditol has the empirical formula HIGH _{2 [} CH (OH) _n] CH ₂ OH, R _{1 is} -OCH ₂ [CH (OH) _n ] CH ₂ OH, or HIGH ₂ [CH (OH) _n ] [CH (OR ₁ )] CH ₂ OH with n = 2-5, wherein R _{1 is} an optionally substituted sugar residue.

Preferably, the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, and mixtures thereof. More preferably, the at least one preferred alditol is selected from the group consisting of erythritol, mannitol, isomalt, maltitol, and mixtures thereof. Most preferably, the at least one alditol is mannitol.

103 Erythrit (Erythritol)

120-123 Isomalt (Palatinit)

145-150 (Gemisch) Galactit (Galactinol)

185-188 Lactit (Lactitol)

146 Maltit (Maltitol)

149-152 Mannit (Mannitol)

166-168 Ribit (Ribitol)

102 Sorbit (Sorbitol)

94-96 The structures and fixed points of these preferred alditols are shown in Table 1 below. description Chemical structure Fixed point [° C] Arabitol (arabitol)

103 Erythritol (erythritol)

120-123 Isomalt (Palatinit)

145-150 (mixture) Galactitol (galactinol)

185-188 Lactitol (lactitol)

146 Maltitol (Maltitol)

149-152 Mannitol (mannitol)

166-168 Ribitol

102 Sorbitol (sorbitol)

94-96

Alternatively or in addition to the aforementioned alditols, in the process according to the invention (or for the purposes of the plastic composition according to the invention, the molding composition or the molding or the stabilizer composition), cyclitols, d. H. annular polyols can be used.

In particular, the at least one cyclitol may be selected from the group consisting of inositol, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, quebrachitol, quinic acid, shikimic acid and valalene.

For the purposes of the present invention, the alditols or cyclitols contained as components (B) are considered in terms of their weight fraction as a whole as component (B), so that it is always to understand the entirety of the alditols and / or cyclitols contained.

A particularly preferred variant of the method according to the invention is characterized in that at least one primary antioxidant and at least one secondary antioxidant are introduced into the halogen-free thermoplastic material. This means that as component (A) at least one primary antioxidant and at least one secondary antioxidant are used. In this way, an even more effective stabilization of the halogen-free thermoplastic against oxidative, thermal and / or actinic degradation can be achieved.

In a further preferred variant of the process according to the invention, component (A) and component (B) are in a weight ratio of from 5:95 to 95: 5, preferably from 10:90 to 90:10, particularly preferably from 20:80 to 80 : 20, introduced into the halogen-free thermoplastic recycled material.

If component (A) consists of both a primary antioxidant and a secondary antioxidant, the ratio between primary and secondary antioxidant is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and most preferably 70: 30 to 30:70.

A further preferred variant of the method according to the invention is characterized in that the components (A) and (B) are introduced into the halogen-free thermoplastic polymer recyclate in that the solid components (A) and (B) present as solid present halogen-free thermoplastic polymer recyclate are mixed and the resulting mixture is melted and then cooled, or the present as solid components (A) and (B) melted and the resulting melt is introduced into a melt of the halogen-free thermoplastic polymer recyclate.

Preferably, the components (A) and (B), which may be in the form of powder, granules, solution or flakes, are mixed with the polymer to be stabilized, the polymer matrix is transferred to the melt and then cooled. Alternatively, it is also possible to incorporate the additive in a molten state into a polymer melt.

In the event that further ingredients are added to the halogen-free thermoplastic resin recyclate, they may be added to the polymers separately, in the form of liquids, powders, granules or compacted products or together with the additive composition according to the invention as described above.

In addition, at least one additive which is selected from the group comprising UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropic agents, can preferably additionally be introduced into the halogen-free thermoplastic polymer recyclate. Chain extenders, optical brighteners, antimicrobial agents, antistatics, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, coupling agents, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor scavengers, marking agents, antifogging agents, fillers, Reinforcing materials and mixtures thereof.

1. a) Säurefängern, vorzugsweise Calciumstearat, Magnesiumstearat, Zinkstearat, Aluminiumstearat, Calciumstearat, Calciumlactat, Calciumstearoyl-2-lactat, Hydrotalcite, insbesondere synthetische Hydrotalciten auf Aluminium-, Magnesium- und Zinkbasis, Hydrocalumite, Zeolithe, Erdalkalioxide, insbesondere Calciumoxid und Magnesiumoxid, Erdalkalicarbonate, insbesondere Calciumcarbonat, Magnesiumcarbonat und Dolomit, und Hydroxide, insbesondere Brucit,
2. b) Lichtstabilisatoren, vorzugsweise Lichtstabilisatoren aus der Gruppe der gehinderten Amine,
3. c) Dispergiermitteln,
4. d) Füllstoffdesaktivatoren, und

Furthermore, it is preferred that in the halogen-free thermoplastic polymer recyclate additionally at least one additive is introduced, which is selected from the group consisting of

1. a) Acid scavengers, preferably calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, calcium lactate, calcium stearoyl-2-lactate, hydrotalcites, especially aluminum, magnesium and zinc synthetic hydrotalcites, hydrocalumites, zeolites, alkaline earth oxides, especially calcium oxide and magnesium oxide, alkaline earth carbonates, especially calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite,
2. b) light stabilizers, preferably light stabilizers from the group of hindered amines,
3. c) dispersants,
4. d) filler deactivators, and

Mixtures thereof.

Suitable light stabilizers are, for example, compounds based on 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2- (2-hydroxyphenyl) -1,3,5-triazines.

Examples of suitable 2- (2'-hydroxyphenyl) benzotriazoles are 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5 '-Di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3'-sec- Butyl 5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl ) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxy -carbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 '-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl ) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy -5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'- Dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1 , 1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO-CH ₂ CH ₂ - ₂ , wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy 3 '- (α, α-dimethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) -phenyl] benzotriazole, 2- [2'-hydroxy-3 '- (1,1,3,3 tetramethylbutyl) -5 '- (α, α-dimethylbenzyl) phenyl] benzotriazole.

Suitable 2-hydroxybenzophenones are, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4 , 4'-Dimethoxy derivatives of 2-hydroxybenzophenones.

Suitable acrylates are, for example, ethyl-α-cyano-β, β-diphenylacrylate, isooctyl-α-cyano-β, β-diphenylacrylate, methyl-α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl 4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di- tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) -oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2-ethoxy-2 '-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxydisubstituted oxanilides and mixtures of o- and p-ethoxydisubstituted oxanilides.

Suitable 2- (2-hydroxyphenyl) -1,3,5-triazines are, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy) 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-methylphenyl-1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5 triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxybenzoyl) 3-butyloxypropoxy) -phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] - 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4 -dimethyl-phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) -phenyl] -4,6-bis (2,4-dimethylphenyl-1, 3,5-triazine, 2- (2-hydroxy-4-hexyloxy) -phenyl-4,6-diphenyl-1,3,5-triazine n, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy ) -phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl-1,3,5-triazine.

Examples of suitable metal deactivators are N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicyloyl) oxylyldihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

Examples of suitable hindered amines are 1,1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebazate, bis (1 octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecyl-aminopiperidine, bis (1-acyl-2,2, 6,6-tetramethylpiperidin-4-yl) sebacate 1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) 4-oxo-2,2,6,6-tetramethylpiperidine, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) -succinate, N, N'-bis-formyl-N, N'-bis ( 2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, (33a) bis (1-undecanyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6 -pentamethyl-4-aminopiperidine, 2-undecyl-7, 7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane-tris (2,2,6 , 6-tetramethyl-4-pyridyl) nitrilotriacetate 1,1 '- (1,2-ethanediyl) -bis (3,3,5,5-tetramethyl-piperazinone), 3-n-octyl-7, 7.9, 9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-tria zaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1, 2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -n-butyl-3,5-di tert-butyl-4-hydroxy-benzylmalonate, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis ( 2, 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-) piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '- (1,2-ethanediyl) -bis (3,3, 5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N, N'-bis (2,2 , 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-o xa-3,8-diaza-4-oxospiro- [4,5] decane and epichlorohydrin.

Included in the above structures are in each case also the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N-cyclohexyloxy and the N- (2-hydroxy-2-methylpropoxy) analogs. Furthermore, the following polymeric compounds are included by way of example:

In the aforementioned compounds, n is 1 to 15 in each case.

• Polyacrylate, z.B. Copolymere mit langkettigen Seitengruppen, Polyacrylat-Blockcopolymere, Alkylamide: z.B. N,N'-1,2-Ethandiylbisoctadecanamid Sorbitanester, z.B. Monostearylsorbitanester, Titanate und Zirconate, reaktive Copolymere mit funktionellen Gruppen z.B. Polypropylen-co-Acrylsäure, Polypropylen-co-Maleinsäureanhydrid, Polyethylen-co-Glycidylmethacrylat, Polystyrol-alt-Maleinsäureanhydrid-Polysiloxane: z.B. Dimethylsilandiol-Ethylenoxid Copolymer, Polyphenylsiloxan Copolymer, Amphiphile Copolymere: z.B. Polyethylen-block-Polyethylenoxid, Dendrimere, z.B. hydroxylgruppenhaltige Dendrimere.

Suitable dispersants are, for example:

• Polyacrylates, eg copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: eg N, N'-1,2-ethanediylbisoctadecanamide sorbitan esters, eg monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups eg polypropylene-co-acrylic acid, polypropylene co-acrylic Maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-old-maleic anhydride-polysiloxanes: eg dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: for example polyethylene-block-polyethylene oxide, dendrimers, eg hydroxyl-containing dendrimers.

Suitable nucleating agents include talc, alkali or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such. Benzoic acid, succinic acid, adipic acid, e.g. Sodium benzoate, zinc glycerolate, aluminum hydroxy-bis (4-tert-butyl) benzoate, benzylidene sorbitols, e.g. 1,3: 2,4-bis (benzylidene) sorbitol or 1,3: 2,4-bis (4-methylbenzylidene) sorbitol, 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, as well as trisamides and diamides such as Trimesic acid tricyclohexylamine, trimesic acid tri (4-methylcyclohexylamide), tris (tri (t-butyl amide), N, N ', N "-1,3,5-benzenetriyl tris (2,2-dimethylpropanamide) or 2,6-naphthalenedicarboxylic acid dicyclohexylamide.

Suitable antinucleating agents include, for example, azine dyes, e.g. Nigrosine, ionic liquids and / or lithium salts.

1. a) Anorganische Flammschutzmittel wie z.B. Al(OH)₃, Mg(OH)₂, AlO(OH), MgCO₃, Schichtsilikate wie z.B. Montmorillonit oder Sepiolit, nicht oder organisch modifiziert, Doppelsalze, wie z.B. Mg-Al-Silikate, POSS-(Polyhedral Oligomeric Silsesquioxane) Verbindungen, Huntit, Hydromagnesit oder Halloysit sowie Sb₂O₃, Sb₂O₅, MoO₃, Zinkstannat, Zinkhydroxystannat,
2. b) Stickstoffhaltige Flammschutzmittel wie z.B. Melamin, Melem, Melam, Melon, Melaminderivate, Melaminkondensationsprodukte oder Melaminsalze, Benzoguanamin, Polyisocyanurate, Allantoin, Phosphacene, insbesondere Melamincyanurat, Melaminphosphat, Dimelaminphosphat, Melaminpyrophosphat, Melaminpolyphosphat, Melamin-Metall-Phosphate wie z.B. Melaminaluminiumphosphat, Melaminzinkphosphat, Melaminmagnesiumphosphat, sowie die entsprechenden Pyrophosphate und Polyphosphate, Poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazin], Ammoniumpolyphosphat, Melaminborat, Melaminhydrobromid,
3. c) Radikalbildner, wie z.B. Alkoxyamine, Hydroxylaminester, Azoverbindungen, Sulfenamide, Sulfenimide, Dicumyl oder Polycumyl, Hydroxyimide und deren Derivate wie z.B. Hydroxyimidester oder Hydroxyimidether
4. d) Phosphorhaltige Flammschutzmitteln wie z.B. roter Phosphor, Phosphate wie z.B. Resorcindiphosphat, Bisphenol-A-diphosphat und ihre Oligomere, Triphenylphosphat, Ethylendiamindiphosphat, Phosphinate wie z.B. Salze der hypophosphorigen Säure und Ihrer Derivate wie Alkylphosphinatsalzen z.B. Diethylphosphinataluminium oder Diethylphosphinat-Zink oder Aluminiumphosphinat, Aluminiumphosphit, Aluminiumphosphonat, Phosphonatester, oligomere und polymere Derivate der Methanphosphonsäure, 9,10-Dihydro-9-oxa-10-phosphorylphenanthren-10-oxid (DOPO) und deren substituierte Verbindungen,
5. e) Halogenhaltige Flammschutzmittel auf Chlor- und Brombasis wie z.B. polybrominierte Diphenyloxide, wie z.B. Decabromdi-phenyloxid,Tris(3-bromo-2,2-bis(bromomethyl)propyl-phosphat, Tris(tribromneopentyl)phosphat, Tetrabromphthalsäure, 1,2-Bis-(tribromphenoxy)ethan, Hexabromcyclododecan, bromiertes Diphenylethan, Tris-(2,3-dibrompropyl)isocyanurat, Ethylen-bis-(tetrabromophthalimid), Tetrabromo-bisphenol A, bromiertes Polystyrol, bromiertes Polybutadien bzw, Polystyrol-bromiertes Polybutadien-Copolymere, bromierter Polyphenylenether, bromiertes Epoxidharz, Polypentabrombenzylacrylat, ggf. in Kombination mit Sb₂O₃ und/oder Sb₂O₅,
6. f) Borate wie z.B. Zinkborat oder Calciumborat, ggf. auf Trägermaterial wie z.B. Silica
7. g) Schwefelhaltige Verbindungen wie z.B. elementarer Schwefel, Disulfide und Polysulfide, Thiuramsulfid, Dithiocarbamate, Mercaptobenzthiazol und Sulfenamide,
8. h) Antidrip-Mitteln wie z.B. Polytetrafluorethylen,
9. i) Siliciumhaltige Verbindungen wie z.B. Polyphenylsiloxane,
10. j) Kohlenstoffmodifikationen wie z.B. Carbon-Nanoröhren (CNT), Blähgraphit oder Graphen
11. k) sowie Kombinationen oder Mischungen hieraus.

Suitable flame retardants are, for example:

1. a) Inorganic flame retardants such as Al (OH) ₃ , Mg (OH) ₂ , AlO (OH), MgCO ₃ , phyllosilicates such as montmorillonite or sepiolite, not or organically modified, double salts such as Mg-Al silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite and also Sb ₂ O ₃ , Sb ₂ O ₅ , MoO ₃ , zinc stannate, zinc hydroxystannate,
2. b) Nitrogen-containing flame retardants, for example melamine, melem, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates, such as melamine aluminum phosphate, melamine zinc phosphate, Melamine magnesium phosphate, and the corresponding pyrophosphates and polyphosphates, poly [2,4- (piperazin-1,4-yl) -6- (morpholin-4-yl) -1,3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide .
3. c) radical formers, such as, for example, alkoxyamines, hydroxylamine esters, azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and derivatives thereof, for example hydroxyimide esters or hydroxyimid ethers
4. d) Phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and its derivatives such as alkylphosphinate salts such as diethylphosphine aluminum or diethylphosphinate zinc or aluminum phosphinate, aluminum phosphite, Aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methane phosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,
5. e) Chlorine- and bromine-based halogen-containing flame retardants, such as, for example, polybrominated diphenyl oxides, such as, for example, decabromodiphenyl oxide, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, tris (tribromoneopentyl) phosphate, tetrabromophthalic acid, 1,2- Bis (tribromophenoxy) ethane, hexabromocyclododecane, brominated diphenylethane, tris (2,3-dibromopropyl) isocyanurate, ethylene bis (tetrabromophthalimide), tetrabromo bisphenol A, brominated polystyrene, brominated polybutadiene or polystyrene-brominated polybutadiene Copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl acrylate, optionally in combination with Sb ₂ O ₃ and / or Sb ₂ O ₅ ,
6. f) Borates such as zinc borate or calcium borate, optionally on a support material such as silica
7. g) Sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides,
8. h) antidrip agents such as polytetrafluoroethylene,
9. i) silicon-containing compounds such as polyphenylsiloxanes,
10. j) Carbon modifications such as carbon nanotubes (CNT), expanded graphite or graphene
11. k) as well as combinations or mixtures thereof.

Suitable fillers and reinforcing agents are, for example, synthetic or natural materials such as e.g. Calcium carbonate, silicates, glass fibers, glass beads (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour or fibers of natural products such as e.g. Cellulose or synthetic fibers. Other suitable fillers are hydrotalcites or zeolites or phyllosilicates, e.g. Montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.

Suitable pigments may be inorganic or organic in nature. Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black; organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones. Other suitable pigments are metal-based effect pigments or metal oxide-based pearlescent pigments.

Suitable chain extenders for the linear molecular weight buildup of polycondensation polymers such as polyesters or polyamides are, for example, diepoxides, bisoxazolines, bisoxazolones, bisoxazines, diisocyanates, dianhydrides, bisacyl lactams, bismaleimides, dicyanates, carbodiimides. Other suitable chain extenders are polymeric compounds, e.g. Polystyrene-polyacrylate-polyglycidyl (meth) acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.

Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis (styryl) biphenyls and in particular optical brighteners of the formulas:

Examples of suitable filler deactivators are polysiloxanes, polyacrylates, in particular block copolymers, such as polymethacrylic polyalkylene oxide or polyglycidyl (meth) acrylates and their copolymers, for example with styrene, and epoxides, for example of the following structures:

Suitable antistatic agents include, for example, ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers such as e.g. Polyether amides.

Suitable antiozonants are the abovementioned amines, e.g. N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-dicyclohexyl -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'- phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.

Suitable mold release agents are, for example, montan waxes.

The incorporation of the components (A) and (B) and optionally the additional additives in the plastic recyclate can be carried out by conventional processing methods, wherein the polymer is melted and is mixed with the additive composition according to the invention and optionally further additives, preferably by mixers, kneaders and extruders. Preferred processing machines are extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with a vacuum degassing. The processing can be carried out under air or under inert gas conditions if necessary.

Further, the components (A) and (B) may be prepared and incorporated in the form of so-called masterbatches or concentrates containing, for example, 10-90% of a stabilizer composition consisting of the components (A) and (B) in a polymer.

• a) rezyklierten Polymeren aus Olefinen oder Diolefinen, wie z.B. Polyethylen, insbesondere LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE und UHMWPE, Metallocen-PE (m-PE), Polypropylen, Poylisobutylen, Poly-4-methyl-penten-1, Polybutadien, Polyisopren, Polycycloocten, Polyalkylen-Kohlenmonoxid-Copolymeren, sowie entsprechenden Copolymeren in Form von statistischen oder Blockstrukturen wie z.B. Polypropylen-Polyethylen (EP), EPM oder EPDM, Ethylen-Vinylacetat (EVA), Ethylen-Acrylester, wie z.B. Ethylen-Butylacrylat, EthylenAcrylsäure-Glycidylacrylat, und entsprechenden Propfpolymeren wie z.B. Polypropylen-g-Maleinsäureanhydrid, Polypropylen-g-Acrylsäure und Polyethylen-g-Acrylsäure,
• b) rezykliertem Polystyrol, Polymethylstyrol, Polyvinylnaphthalin, Styrol-Butadien (SB), Styrol-Butadien-Styrol (SBS), Styrol-Ethylen-Butylen-Styrol (SEBS), Styrol-Ethylen-Propylen-Styrol, Styrolisopren, Styrol-Isopren-Styrol (SIS), Styrol-butadien-acrylnitril (ABS), Styrol-acrylnitril-acrylat (ASA), Styrol-Ethylen, Styrol-Maleinsaureanhydrid-Polymeren einschließlich entsprechenden Pfropfcopolymeren wie z.B. Styrol auf Butadien, Maleinsäureanhydrid auf SBS oder SEBS, sowie Pfropfcopolymeren aus Methylmethacrylat, Styrol-Butadien und ABS (MABS),
• c) rezyklierten Polymeren von ungesättigten Estern wie z.B. Polyacrylate und Polymethacrylate wie Polymethylmethacrylat (PMMA), Polybutylacrylat, Polylaurylacrylat, Polystearylacrylat, Polyacrylnitril, Polyacrylamide, und entsprechenden Copolymeren wie z.B. Polyacrylnitril-Polyalkylacrylat,
• d) rezyklierten Polymeren aus ungesättigten Alkoholen und Derivaten, wie z.B. Polyvinylalkohol, Polyvinylacetat, Polyvinylbutyral,
• e) rezyklierten Polyacetalen, wie z.B. Polyoxymethylen (POM), und entsprechenden Copolymeren, wie z.B. Copolymere mit Butanal,
• f) rezyklierten Polyphenylenoxiden und Blends von diesen mit Polystyrol oder Polyamiden,
• g) rezyklierten Polymeren von cyclischen Ethern wie z.B. Polyethylenglycol, Polypropylenglycol, Polyethylenoxid, Polypropylenoxid,
• h) rezyklierten Polyurethanen aus hydroxyterminierten Polyethern oder Polyestern und aromatischen oder aliphatischen Isocyanaten, insbesondere lineare Polyurethane, Polyharnstoffen,
• i) rezyklierten Polyamiden wie z.B. Polyamid-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, Polyamid 11, Polyamid 12 sowie (teil-)aromatische Polyamide wie z.B. Polyphthalamide, z.B. hergestellt aus Terephthalsäure und/oder Isophthalsäure und aliphatischen Diaminen oder aus aliphatischen Dicarbonsäuren wie z.B. Adipinsäure oder Sebazinsäure und aromatischen Diaminen wie z.B. 1,4- oder 1,3-Diaminobenzol,
• j) rezyklierten Polyimiden, Polyamid-imiden, Polyetherimiden, Polyesterimiden, Poly(ether)ketonen, Polysulfonen, Polyethersulfonen, Polyarylsulfonen, Polyphenylensulfid, Polybenzimidazolen, Polyhydantoinen,
• k) rezyklierten Polyestern aus aliphatischen oder aromatischen Dicarbonsäuren und Diolen oder aus Hydroxy-Carbonsäuren wie z.B. Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polypropylenterphthalat, Polyethylennaphthylat, Poly-1,4-dimethylocyclohexanterphthalat, Polyhydroxybenzoat, Polyhydroxynaphthalat, Polymilchsäure,
• l) rezyklierten Polycarbonaten, Polyestercarbonaten, sowie Blends von diesen wie z.B. PC/ABS, PC/PBT, PC/PET/PBT,
• m) rezyklierten Cellulosederivaten, wie z.B. Cellulosenitrat, Celluloseacetat, Cellulosepropionat, Cellulosebutyrat,
• n) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymere.

Furthermore, it is preferable that the halogen-free thermoplastic resin recyclate is selected from the group consisting of

• a) recycled polymers of olefins or diolefins, such as polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1 , Polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and corresponding copolymers in the form of random or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters, such as ethylene Butyl acrylate, ethylene acrylic acid glycidyl acrylate, and corresponding graft polymers such as polypropylene g-maleic anhydride, polypropylene g acrylic acid and polyethylene g acrylic acid,
• b) recycled polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene Styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, and graft copolymers Methylmethacrylate, styrene-butadiene and ABS (MABS),
• c) recycled polymers of unsaturated esters such as polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyacrylonitrile, polyacrylamides, and corresponding copolymers such as polyacrylonitrile-polyalkyl acrylate,
• d) recycled polymers of unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral,
• e) recycled polyacetals, such as polyoxymethylene (POM), and corresponding copolymers, such as copolymers with butanal,
• f) recycled polyphenylene oxides and blends of these with polystyrene or polyamides,
• g) recycled polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide,
• h) recycled polyurethanes of hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas,
• i) recycled polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, for example prepared from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene,
• j) recycled polyimides, polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins,
• k) recycled polyesters of aliphatic or aromatic dicarboxylic acids and diols or of hydroxy carboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylocyclohexanterphthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid,
• l) recycled polycarbonates, polyestercarbonates, and blends thereof, such as PC / ABS, PC / PBT, PC / PET / PBT,
• m) recycled cellulose derivatives, such as, for example, cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate,
• n) and mixtures, combinations or blends of two or more of the aforementioned polymers.

The halogen-free thermoplastic polymer recyclate is particularly preferably selected from the group consisting of polymers of olefins or diolefins, for example polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene PE (m-PE), polypropylene , Poylisobutylen, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and corresponding copolymers in the form of random or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene acrylic esters such as ethylene-butyl acrylate, ethylene-acrylic acid glycidyl acrylate, and corresponding graft polymers such as polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid and polyethylene-g-acrylic acid.

The halogen-free thermoplastic is very particularly preferably a polyolefin, in particular a polyolefin recyclate. For example, the halogen-free thermoplastic material of the recyclate may be polypropylene, in particular a polypropylene recyclate or polyethylene, in particular a polyethylene recyclate.

1. (A) 0,04 bis 6 Gew.-Teile, bevorzugt 0,06 bis 1 Gew.-Teile, mindestens eines primären Antioxidans und/oder mindestens eines sekundären Antioxidans, und
2. (B) 0,02 bis 3 Gew.-Teile, bevorzugt 0,03 bis 0,5 Gew.-Teile, mindestens eines Alditols und/oder mindestens eines Cyclitols

in 91 bis 99,94 Gew.-Teile, bevorzugt 98,5 bis 99,91 Gew.-Teile, mindestens eines halogenfreien thermoplastischen Kunststoff-Rezyklats eingebracht.Preferably, in the process according to the invention

1. (A) 0.04 to 6 parts by weight, preferably 0.06 to 1 part by weight, of at least one primary antioxidant and / or at least one secondary antioxidant, and
2. (B) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one alditol and / or at least one cyclitol

in 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight, of at least one halogen-free thermoplastic material recycled recycled.

• (A1) 0,02 bis 3 Gew.-Teile, bevorzugt 0,03 bis 0,5 Gew.-Teile, mindestens eines primären Antioxidans,
• (A2) 0,02 bis 3 Gew.-Teile, bevorzugt 0,03 bis 0,5 Gew.-Teile, mindestens eines sekundären Antioxidans, und
• (B) 0,02 bis 3 Gew.-Teile, bevorzugt 0,03 bis 0,5 Gew.-Teile, mindestens eines Alditols und/oder mindestens eines Cyclitols

in 91 bis 99,94 Gew.-Teile, bevorzugt 98,5 bis 99,91 Gew.-Teile, mindestens eines halogenfreien thermoplastischen Kunststoff-Rezyklats eingebracht werden.Furthermore, it is preferred that

• (A1) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one primary antioxidant,
• (A2) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one secondary antioxidant, and
• (B) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one alditol and / or at least one cyclitol

in 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight, of at least one halogen-free thermoplastic synthetic material recycled.

1. (A) mindestens einem primären Antioxidans und/oder mindestens einem sekundären Antioxidans,
2. (B) mindestens einem Alditol und/oder mindestens einem Cyclitol, und
3. (C) mindestens einem halogenfreien thermoplastischen Kunststoff-Rezyklat.

In addition, the present invention also relates to a plastic composition containing or consisting of

1. (A) at least one primary antioxidant and / or at least one secondary antioxidant,
2. (B) at least one alditol and / or at least one cyclitol, and
3. (C) at least one halogen-free thermoplastic plastic recyclate.

1. (A) 0,04 bis 6 Gew.-Teile, bevorzugt 0,06 bis 1 Gew.-Teile, mindestens eines primären Antioxidans und/oder mindestens eines sekundären Antioxidans,
2. (B) 0,02 bis 3 Gew.-Teile, bevorzugt 0,03 bis 0,5 Gew.-Teile, mindestens eines Alditols, und
3. (C) 91 bis 99,94 Gew.-Teile, bevorzugt 98,5 bis 99,91 Gew.-Teile, mindestens eines halogenfreien thermoplastischen Kunststoffs

enthält oder hieraus besteht.In a preferred embodiment, the plastic composition is characterized in that the plastic composition

1. (A) 0.04 to 6 parts by weight, preferably 0.06 to 1 part by weight, of at least one primary antioxidant and / or at least one secondary antioxidant,
2. (B) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one alditol, and
3. (C) 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight, of at least one halogen-free thermoplastic

contains or consists of.

Preferably, the composition of the invention contains at least one primary antioxidant and at least one secondary antioxidant.

• (A1) 0,02 bis 3 Gew.-Teile, bevorzugt 0,03 bis 0,5 Gew.-Teile, mindestens eines primären Antioxidans,
• (A2) 0,02 bis 3 Gew.-Teile, bevorzugt 0,03 bis 0,5 Gew.-Teile, mindestens eines sekundären Antioxidans,
• (B) 0,02 bis 3 Gew.-Teile, bevorzugt 0,03 bis 0,5 Gew.-Teile, mindestens eines Alditols und/oder mindestens eines Cyclitols, und
• (C) 91 bis 99,94 Gew.-Teile, bevorzugt 98,5 bis 99,91 Gew.-Teile, mindestens eines halogenfreien thermoplastischen Kunststoff-Rezyklats.

enthält oder hieraus besteht.A further preferred embodiment is characterized in that the plastic composition

• (A1) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one primary antioxidant,
• (A2) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one secondary antioxidant,
• (B) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one alditol and / or at least one cyclitol, and
• (C) 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight, of at least one halogen-free thermoplastic plastic recyclate.

contains or consists of.

According to a further preferred embodiment, the plastic composition according to the invention additionally comprises at least one additive which is selected from the group consisting of UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, tougheners, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, optical brighteners, antimicrobial agents, antistatics, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, coupling agents, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor scavengers, marking agents, antifogging agents, fillers, reinforcing agents and Mixtures thereof.

1. a) Säurefängern, vorzugsweise Calciumstearat, Magnesiumstearat, Zinkstearat, Aluminiumstearat, Calciumstearat, Calciumlactat, Calciumstearoyl-2-lactat, Hydrotalcite, insbesondere synthetische Hydrotalciten auf Aluminium-, Magnesium- und Zinkbasis, Hydrocalumite, Zeolithe, Erdalkalioxide, insbesondere Calciumoxid und Magnesiumoxid, Erdalkalicarbonate, insbesondere Calciumcarbonat, Magnesiumcarbonat und Dolomit, und Hydroxide, insbesondere Brucit,
2. b) Lichtstabilisatoren, vorzugsweise Lichtstabilisatoren aus der Gruppe der gehinderten Amine,
3. c) Dispergiermitteln,
4. d) Füllstoffdesaktivatoren, und

Mischungen hiervon.Furthermore, it is preferred that the plastic composition additionally contains at least one additive which is selected from the group consisting of

1. a) Acid scavengers, preferably calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, calcium lactate, calcium stearoyl-2-lactate, hydrotalcites, especially aluminum, magnesium and zinc synthetic hydrotalcites, hydrocalumites, zeolites, alkaline earth oxides, especially calcium oxide and magnesium oxide, alkaline earth carbonates, especially calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite,
2. b) light stabilizers, preferably light stabilizers from the group of hindered amines,
3. c) dispersants,
4. d) filler deactivators, and

Mixtures thereof.

Preferably, the plastic composition according to the invention can be prepared by a process according to the invention for stabilizing halogen-free thermoplastics against oxidative, thermal and / or actinic degradation or has been prepared therewith.

All of the preferred variants, exemplary embodiments and comments already described with regard to the method according to the invention (for example with respect to possible components and additives to be used) also apply correspondingly to the plastic composition according to the invention.

According to a preferred embodiment of the plastic composition according to the invention, the at least one primary antioxidant is selected from the group consisting of phenolic antioxidants, amines, lactones and mixtures thereof.

Particularly preferred as the primary antioxidant, the phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate contained in the plastic composition of the invention.

A further preferred embodiment of the plastic composition according to the invention is characterized in that the at least one secondary antioxidant is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphonites, organo-sulfur compounds, in particular sulfides and disulfides, and mixtures thereof.

The phosphite tris (2,4-di-tert-butylphenyl) phosphite is particularly preferably contained in the plastic composition according to the invention as a secondary antioxidant.

According to a further preferred embodiment, the at least one alditol has the empirical formula HIGH _{2 [} CH (OH) _n] CH ₂ OH, R _{1 is} -OCH ₂ [CH (OH) _n ] CH ₂ OH, or HIGH ₂ [CH (OH) _n ] [CH (OR ₁ )] CH ₂ OH with n = 2-5, wherein R _{1 is} an optionally substituted sugar residue.

Preferably, the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, and mixtures thereof. More preferably, the at least one preferred alditol is selected from the group consisting of erythritol, mannitol, isomalt, maltitol, and mixtures thereof. Most preferably, the at least one alditol is mannitol.

In a further preferred embodiment, component (A) and component (B) are in a weight ratio of from 5:95 to 95: 5, preferably from 90:10 to 10:90, particularly preferably from 20:80 to 80:20, contained in the plastic composition.

1. a) rezyklierten Polymeren aus Olefinen oder Diolefinen, wie z.B. Polyethylen, insbesondere LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE und UHMWPE, Metallocen-PE (m-PE), Polypropylen, Poylisobutylen, Poly-4-methyl-penten-1, Polybutadien, Polyisopren, Polycycloocten, Polyalkylen-Kohlenmonoxid-Copolymeren, sowie entsprechenden Copolymeren in Form von statistischen oder Blockstrukturen wie z.B. Polypropylen-Polyethylen (EP), EPM oder EPDM, Ethylen-Vinylacetat (EVA), Ethylen-Acrylester, wie z.B. Ethylen-Butylacrylat, EthylenAcrylsäure-Glycidylacrylat, und entsprechenden Propfpolymeren wie z.B. Polypropylen-g-Maleinsäureanhydrid, Polypropylen-g-Acrylsäure und Polyethylen-g-Acrylsäure,
2. b) rezykliertem Polystyrol, Polymethylstyrol, Polyvinylnaphthalin, Styrol-Butadien (SB), Styrol-Butadien-Styrol (SBS), Styrol-Ethylen-Butylen-Styrol (SEBS), Styrol-Ethylen-Propylen-Styrol, Styrolisopren, Styrol-Isopren-Styrol (SIS), Styrol-butadien-acrylnitril (ABS), Styrol-acrylnitril-acrylat (ASA), Styrol-Ethylen, Styrol-Maleinsaureanhydrid-Polymeren einschließlich entsprechenden Pfropfcopolymeren wie z.B. Styrol auf Butadien, Maleinsäureanhydrid auf SBS oder SEBS, sowie Pfropfcopolymeren aus Methylmethacrylat, Styrol-Butadien und ABS (MABS),
3. c) rezyklierten Polymeren von ungesättigten Estern wie z.B. Polyacrylate und Polymethacrylate wie Polymethylmethacrylat (PMMA), Polybutylacrylat, Polylaurylacrylat, Polystearylacrylat, Polyacrylnitril, Polyacrylamide, und entsprechenden Copolymeren wie z.B. Polyacrylnitril-Polyalkylacrylat,
4. d) rezyklierten Polymeren aus ungesättigten Alkoholen und Derivaten, wie z.B. Polyvinylalkohol, Polyvinylacetat, Polyvinylbutyral,
5. e) rezyklierten Polyacetalen, wie z.B. Polyoxymethylen (POM), und entsprechenden Copolymeren, wie z.B. Copolymere mit Butanal,
6. f) rezyklierten Polyphenylenoxiden und Blends von diesen mit Polystyrol oder Polyamiden,
7. g) rezyklierten Polymeren von cyclischen Ethern wie z.B. Polyethylenglycol, Polypropylenglycol, Polyethylenoxid, Polypropylenoxid,
8. h) rezyklierten Polyurethanen aus hydroxyterminierten Polyethern oder Polyestern und aromatischen oder aliphatischen Isocyanaten, insbesondere lineare Polyurethane, Polyharnstoffen,
9. i) rezyklierten Polyamiden wie z.B. Polyamid-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, Polyamid 11, Polyamid 12 sowie (teil-)aromatische Polyamide wie z.B. Polyphthalamide, z.B. hergestellt aus Terephthalsäure und/oder Isophthalsäure und aliphatischen Diaminen oder aus aliphatischen Dicarbonsäuren wie z.B. Adipinsäure oder Sebazinsäure und aromatischen Diaminen wie z.B. 1,4- oder 1,3-Diaminobenzol,
10. j) rezyklierten Polyimiden, Polyamid-imiden, Polyetherimiden, Polyesterimiden, Poly(ether)ketonen, Polysulfonen, Polyethersulfonen, Polyarylsulfonen, Polyphenylensulfid, Polybenzimidazolen, Polyhydantoinen,
11. k) rezyklierten Polyestern aus aliphatischen oder aromatischen Dicarbonsäuren und Diolen oder aus Hydroxy-Carbonsäuren wie z.B. Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polypropylenterphthalat, Polyethylennaphthylat, Poly-1,4-dimethylocyclohexanterphthalat, Polyhydroxybenzoat, Polyhydroxynaphthalat, Polymilchsäure,
12. l) rezyklierten Polycarbonaten, Polyestercarbonaten, sowie Blends von diesen wie z.B. PC/ABS, PC/PBT, PC/PET/PBT,
13. m) rezyklierten Cellulosederivaten, wie z.B. Cellulosenitrat, Celluloseacetat, Cellulosepropionat, Cellulosebutyrat,
14. n) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymere.

Furthermore, it is preferable that the halogen-free thermoplastic resin recyclate is selected from the group consisting of

1. a) recycled polymers of olefins or diolefins, such as polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1 , Polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and corresponding copolymers in the form of random or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters, such as ethylene Butyl acrylate, ethylene acrylic acid glycidyl acrylate, and corresponding graft polymers such as polypropylene g-maleic anhydride, polypropylene g acrylic acid and polyethylene g acrylic acid,
2. b) recycled polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene Styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, and graft copolymers Methylmethacrylate, styrene-butadiene and ABS (MABS),
3. c) recycled polymers of unsaturated esters such as polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyacrylonitrile, polyacrylamides, and corresponding copolymers such as polyacrylonitrile-polyalkyl acrylate,
4. d) recycled polymers of unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral,
5. e) recycled polyacetals, such as polyoxymethylene (POM), and corresponding copolymers, such as copolymers with butanal,
6. f) recycled polyphenylene oxides and blends of these with polystyrene or polyamides,
7. g) recycled polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide,
8. h) recycled polyurethanes of hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas,
9. i) recycled polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, for example prepared from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene,
10. j) recycled polyimides, polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins,
11. k) recycled polyesters of aliphatic or aromatic dicarboxylic acids and diols or of hydroxy carboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylocyclohexanterphthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid,
12. l) recycled polycarbonates, polyestercarbonates, and blends thereof, such as PC / ABS, PC / PBT, PC / PET / PBT,
13. m) recycled cellulose derivatives, such as, for example, cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate,
14. n) and mixtures, combinations or blends of two or more of the aforementioned polymers.

Most preferably, the halogen-free thermoplastic resin recyclate is selected from the group consisting of polymers of olefins or diolefins, e.g. Polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide Copolymers, as well as corresponding copolymers in the form of random or block structures such as Polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters, e.g. Ethylene-butyl acrylate, ethylene-acrylic acid-glycidyl acrylate, and corresponding graft polymers, e.g. Polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid and polyethylene-g-acrylic acid.

The halogen-free thermoplastic polymer recyclate is very particularly preferably a polyolefin, in particular a polyolefin recyclate. For example, the halogen-free thermoplastic material may be polypropylene, in particular a polypropylene recyclate.

The present invention also relates to a molding compound or molding which is preparable from plastic composition according to the invention, in particular in the form of injection molded parts, films, films, paints, coatings, foams, fibers, cables, pipes, profiles, hollow bodies, tapes, membranes, e.g. Geomembranes, lubricants, colorants and / or adhesives, which are prepared by extrusion, injection molding, blow molding, calendering, pressing, spinning processes and / or Rotomoulding example. for the electrical industry, for the construction industry, for the transport industry, for medical applications, for household and electrical appliances, for vehicle parts, for consumer goods, for packaging, for furniture, and / or for textiles.

1. (A) mindestens einem primären Antioxidans und/oder mindestens einem sekundären Antioxidans, und
2. (B) mindestens einem Alditol und/oder mindestens einem Cyclitol.

Furthermore, the present invention also relates to a stabilizer composition for stabilizing halogen-free thermoplastic synthetic recyclates, preferably halogen-free thermoplastic synthetic recyclates, against oxidative, thermal and / or actinic degradation consisting of

1. (A) at least one primary antioxidant and / or at least one secondary antioxidant, and
2. (B) at least one alditol and / or at least one cyclitol.

All of the preferred variants, exemplary embodiments and comments (for example regarding possible components and additives to be used) which have already been described with regard to the method according to the invention and with regard to the inventive plastic composition also apply correspondingly to the stabilizer composition according to the invention.

In a preferred embodiment of the stabilizer composition according to the invention, the at least one primary antioxidant is selected from the group consisting of phenolic antioxidants, amines, lactones and mixtures thereof.

Preferred phenolic antioxidants, preferred amines, and preferred lactones are each the same as those mentioned in the process of the present invention and in the inventive plastic composition.

A further preferred embodiment of the stabilizer composition according to the invention is characterized in that the at least one secondary antioxidant is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphonites, organo-sulfur compounds, in particular sulfides and disulfides, and mixtures thereof.

Preferred phosphites or phosphonites and preferred sulfur compounds are each the same as those mentioned in the inventive method and in the inventive plastic composition.

According to a further preferred embodiment, the at least one alditol has the empirical formula HIGH _{2 [} CH (OH) _n] CH ₂ OH, R _{1 is} -OCH ₂ [CH (OH) _n ] CH ₂ OH, or HIGH ₂ [CH (OH) _n ] [CH (OR ₁ )] CH ₂ OH with n = 2-5, wherein R _{1 is} an optionally substituted sugar residue.

Preferably, the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, and mixtures thereof. More preferably, the at least one preferred alditol is selected from the group consisting of erythritol, mannitol, isomalt, maltitol, and mixtures thereof. Most preferably, the at least one alditol is mannitol.

1. (A) mindestens einem primären Antioxidans und/oder mindestens einem sekundären Antioxidans, und
2. (B) mindestens einem Alditol und/oder mindestens einem Cyclitol.

zur Stabilisierung von halogenfreien thermoplastischen Kunststoffen, vorzugsweise von halogenfreien thermoplastischen Kunststoff-Rezyklaten, gegen oxidativen, thermischen und/oder aktinischen Abbau.The present invention also relates to the use of the stabilizer composition of the invention or a stabilizer composition comprising or consisting of

1. (A) at least one primary antioxidant and / or at least one secondary antioxidant, and
2. (B) at least one alditol and / or at least one cyclitol.

for stabilizing halogen-free thermoplastics, preferably halogen-free thermoplastic synthetic recyclates, against oxidative, thermal and / or actinic degradation.

Preferred halogen-free thermoplastics are the same as those mentioned with respect to the method according to the invention or with respect to the inventive plastic composition.

Particularly preferred is the stabilizer composition for stabilizing polyolefin recyclates
+ used against oxidative, thermal and / or actinic degradation.

All the preferred variants, exemplary embodiments and comments (for example regarding possible components and additives to be used) which have already been described with regard to the inventive method and to the inventive plastic composition and to the stabilizer composition according to the invention also apply correspondingly to the inventive use of a stabilizer composition.

The present invention will be explained in more detail with reference to the following exemplary embodiments without restricting the invention to the parameters specifically shown.

To simulate a recycle in the form of a production waste, a commercial polypropylene (Moplen HP 500N, Lyondell Basell Industries) was ground to a powder and pressed three times at a maximum temperature of 230 ° C by means of a Process 11 (Fisher Scientific) twin-screw extruder at 200 rpm processed, cooled in a water bath and then granulated. This process results in pre-damage resulting in an increase in MVR (Melt Volume Rate measured at 230 ° C / 2.16 kg) as measured by ISO 1133, which correlates with degradation of the polymer. An increase of the MVR from 18.1 g / 10 min (after 1st extrusion) to 25.0 g / 10 min (3rd extrusion) is measured. This increase represents a significant previous damage. Subsequently, this pre-damaged polypropylene was processed in the subsequent 4th extrusion with the stabilizers indicated in Table 2 and the MVR was determined again. Subsequently, the granules obtained were reprocessed without further additives (5th extrusion).
It shows that the non-post-stabilized polymer is still subject to significant degradation. The degradation can be reduced by adding a stabilizer combination of a commercial antioxidant and a phosphite (Comparative Example 2) or a special recyclate stabilizer (Comparative Example 3). Surprisingly, the addition of an alditol (mannitol) to a phenolic antioxidant and a phosphite results in improved stabilization, ie lowest MVR. Another extrusion step shows the best stabilization effect, ie the lowest MVR value by the composition according to the invention. Table 2: Post-stabilization of polypropylene poststabilization After 4th extrusion MVR (230 / 2.16) After 5. extrusion MVR (230 / 2.16) Comparative Example 1 Without addition 29.5 34.6 Comparative Example 2 0.05% AO-1 + 0.05% P-1 23.2 25.4 Comparative Example 3 0.2% Recyclostab 411 23.0 24.4 Inventive Example 1 0.05% AO-1 + 0.05% P-1 + 0.1% mannitol 22.3 24.0 AO-1: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate P-1: tris (2,4-di-tert-butylphenyl) phosphite
Recyclostab 411: Recyclostab 411 is a commercially available stabilizer system which is recommended in particular for polyolefin recyclates (manufacturer: PolyAd Services GmbH, Bensheim, see, in particular, Compounding World, April 2016, 41-48).

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

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• US 6525158 [0004]
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Claims (20)

Process for the stabilization of halogen-free thermoplastic polymer recyclates against oxidative, thermal and / or actinic degradation, in which (A) at least one primary antioxidant and / or at least one secondary antioxidant, and (B) at least one alditol and / or at least one cyclitol, are introduced into a halogen-free thermoplastic plastic recyclate. Method according to Claim 1 , characterized in that the at least one primary antioxidant is selected from the group consisting of phenolic antioxidants, amines, lactones and mixtures thereof. Method according to one of the preceding claims, characterized in that the at least one secondary antioxidant is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphonites, organo-sulfur compounds, in particular sulfides and disulfides, and mixtures thereof. Method according to one of the preceding claims, characterized in that the at least one alditol is the empirical formula HIGH _{2 [} CH (OH) _n] CH ₂ OH, R _{1 is} -OCH ₂ [CH (OH) _n ] CH ₂ OH, or HIGH ₂ [CH (OH) _n ] [CH (OR ₁ )] CH ₂ OH with n = 2-5, wherein R _{1 is} an optionally substituted sugar residue. A method according to any one of the preceding claims, characterized in that the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol and mixtures thereof, wherein the at least an alditol is preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol, and mixtures thereof. Method according to one of the preceding claims, characterized in that the at least one cyclitol is selected from the group consisting of inositol, Quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, Quebrachitol, quinic acid, shikimic acid and Valienol. Method according to one of the preceding claims, characterized in that at least one primary antioxidant and at least one secondary antioxidant are introduced into the halogen-free thermoplastic polymer recyclate. Method according to one of the preceding claims, characterized in that the component (A) and the component (B) in a weight ratio of 5:95 to 90:10, preferably from 10:90 to 90:10, particularly preferably from 20:80 to 80:20, are introduced into the halogen-free thermoplastic resin recyclate. Method according to one of the preceding claims, characterized in that the components (A) and (B) are introduced into the halogen-free thermoplastic polymer recyclate in that the present as solid components (A) and (B) with the present as a solid halogen-free thermoplastic polymer recyclate are mixed and the resulting mixture is melted and then cooled, or the present as a solid components (A) and (B) melted and the resulting melt is introduced into a melt of the halogen-free thermoplastic polymer recyclate. A method according to any one of the preceding claims, characterized in that the halogen-free thermoplastic resin recyclate is selected from the group consisting of a) recycled polymers of olefins or diolefins, such as polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and corresponding copolymers in the form of random or block structures such as polypropylene Polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters such as ethylene-butyl acrylate, ethylene-acrylic acid-glycidyl acrylate, and corresponding graft polymers such as polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid and polyethylene-g Acrylic acid, b) recycled polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene Isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, and graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), c) recycled polymers of unsaturated esters such as polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, poly d) recycled polymers of unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, e) recycled polyacetals, such as polyoxymethylene (POM), and corresponding copolymers, such as g) recycled polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, h) recycled polyurethanes of hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas, i) recycled polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, for example prepared from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, j) recycled polyimides, polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyethersulfones , Polyarylsulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins, k) recycled polyesters of aliphatic or aromatic dicarboxylic acids and diols or from hydroxy-carboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylocyclohexanterphthalat, polyhydroxybenzoate , Polyhydroxynaphthalate, polylactic acid, l) recycled polycarbonates, polyestercarbonates, and blends thereof, such as PC / ABS, PC / PBT, PC / PET / PBT, m) recycled cellulose derivatives, such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, n) and Blends, combinations or blends of two or more more of the aforementioned polymers. Plastic composition containing or consisting of (A) at least one primary antioxidant and / or at least one secondary antioxidant, (B) at least one alditol and / or at least one cyclitol, and (C) at least one halogen-free thermoplastic plastic recyclate. Plastic composition according to the preceding claim, characterized in that the plastic composition (A) contains 0.04 to 6 parts by weight, preferably 0.06 to 1 part by weight, of at least one primary antioxidant and / or at least one secondary antioxidant, (B) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one alditol and / or at least one cyclitol, and (C) 91 to 99.94 parts by weight, preferably 98, 5 to 99.91 parts by weight, contains or consists of at least one halogen-free thermoplastic plastic recyclate. Plastic composition according to one of the two preceding claims, characterized in that the plastic composition (A1) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one primary antioxidant, (A2) 0, 02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one secondary antioxidant, (B) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight. Parts, at least one alditol and / or at least one cyclitol, and (C) 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight, contains or consists of at least one halogen-free thermoplastic plastic recyclate , Plastic composition according to one of Claims 11 to 13 characterized in that the plastic composition additionally contains at least one additive selected from the group consisting of UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, optical Brighteners, antimicrobial agents, antistatics, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, coupling agents, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor scavengers, marking agents, antifogging agents, fillers, reinforcing agents and blends hereof. Plastic composition according to one of Claims 11 to 14 , characterized in that the plastics composition additionally contains at least one additive selected from the group consisting of a) acid scavengers, preferably calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, calcium lactate, calcium stearoyl-2-lactate, hydrotalcites, in particular synthetic hydrotalcites Aluminum, magnesium and zinc base, hydrocalumites, zeolites, alkaline earth oxides, in particular calcium oxide and magnesium oxide, alkaline earth carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite, b) light stabilizers, preferably light stabilizers from the group of hindered amines, c) dispersants , d) filler deactivators, and e) mixtures thereof. Plastic composition according to one of Claims 11 to 15 , characterized in that the at least one halogen-free thermoplastic polymer recyclate is preferably a polyolefin recyclate. Plastic composition according to one of Claims 11 to 16 , characterized in that the plastic composition with a method according to any of Claims 1 to 10 can be produced. Molding composition or molding produced from a plastic composition according to one of Claims 11 to 17 , in particular in the form of injection-molded parts, films, films, lacquers, coatings, foams, fibers, cables, pipes, profiles, hollow bodies, tapes, membranes, for example geomembranes, lubricants, colorants and / or adhesives, via extrusion, injection molding, blow molding, Calendering, pressing processes, spinning processes and / or Rotomoulding are manufactured eg for the electrical industry, for the construction industry, for the transport industry, for medical applications, for household and electrical appliances, for vehicle parts, for consumer goods, for packaging, for furniture, and / or for Textiles. Stabilizer composition for stabilizing halogen-free thermoplastic synthetic recyclates against oxidative, thermal and / or actinic degradation, consisting of (A) at least one primary antioxidant and / or at least one secondary antioxidant, and (B) at least one alditol and / or at least one cyclitol. Use of a stabilizer composition containing or consisting of (A) at least one primary antioxidant and / or at least one secondary antioxidant, and (B) at least one alditol and / or at least one cyclitol for the stabilization of halogen-free thermoplastic synthetic recyclates against oxidative, thermal and / or actinic degradation.